Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/5205—Salts of P-acids with N-bases
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2

Definitions

• This invention relates to self-extinguishing polymeric compositions based on thermoplastic polymers or polymers with elastomeric properties, especially olefinic polymers or copolymers, containing salts of triazine compounds in combination with ammonium or amine phosphates and/or phosphonates.
• Intumescent formulations generally consist of the polymer and at least three main additives, of which one is essentially phosphorated, its purpose being to form during combustion an impermeable semi-solid vitreous layer consisting essentially of polyphosphoric acid, and to activate the intumescence formation process, a second contains nitrogen for foaming purposes and the third contains carbon acting as a carbon donor for forming an insulating cellular layer (char) between the polymer and the flame.
• intumescent formulations of this type are those described in the following patents: USA 3,810,862 (Phillips Petroleum Co.) based on melamine, pentaerythritol and ammonium polyphosphate, USA 4,727,102 (Vamp S.r.l.) based on melamine cyanurate, a hydroxyalkyl derivative of isocyanuric acid and ammonium polyphosphate, and published patent application WO 85/05626 (Plascoat U.K. Limited) based on various phosphorus and nitrogen compounds, and in particular a combination of melamine phosphate, pentaerythritol and ammonium polyphosphate.
• a nitrogen-containing organic compound is used, generally an aminoplastic resin obtained by condensing urea, melamine or dicyandiamide with formaldehyde.
• Self-extinguishing compositions can also be obtained by using single component additives containing both nitrogen and phosphorus in the organic molecule, as described in USA patent 4,201,705 (Borg-Warner Corp.).
• intumescence retarding systems give the polymer containing them the property of forming a carbon residue following fire or the application of a flame.
• Retarding systems of this type have numerous advantages, including the absence of corrosion in the machines used to work the polymers, lower smoke emission than systems containing metal compounds and halogenated hydrocarbons, and in particular the possibility of achieving satisfactory flame retardant properties in the polymer with a smaller total quantity of additive and hence without excessive fall-off in the polymer mechanical properties.
• the Applicant has now found that the saline compounds of the present invention, in conjunction with only the phosphorated component, enable intumescent polymer compositions to be obtained characterized by good thermal stability both towards thermal oxidation and during the transformation stage, so enabling them to be worked at a higher temperature than in the known art.
• the polymeric compositions of the present invention also have the advantage of producing only very moderate, non obscuring smoke emission in the case of a fire.
• compositions of the present invention comprise:
• R to R5 which can be the same or different, have the aforesaid meaning or are: H; C1-C18 alkyl; C2-C8 alkenyl; C6-C16 cycloalkyl or alkylcycloalkyl, possibly substituted with a hydroxyl or C1-C4 hydroxyalkyl function.
• radicals from R to R5 in general formula (I) are: methyl; ethyl; propyl; isopropyl; n-butyl; isobutyl; tert-butyl; n-pentyl; isopentyl; n-hexyl; tert-hexyl; octyl; tert-octyl; decyl; dodecyl; octadecyl; ethenyl; propenyl; butenyl; isobutenyl; hexenyl; octenyl; cyclohexyl; propylcyclohexyl; butylcyclohexyl; decylcyclohexyl; hydroxycyclohexyl; hydroxyethylcyclohexyl; 2-hydroxyethyl; 2-hydroxypropyl; 3-hydroxypropyl; 3-hydroxybutyl; 4-hydroxybutyl
• heterocyclic radicals which can replace the groups: in general formula (I) are: aziridine; pyrrolidine; piperidine; morpholine; thiomorpholine; piperazine; 4-methylpiperazine; 4-ethylpiperazine; 2-methylpiperazine; 2,5-dimethylpiperazine; 2,3,5,6-tetramethylpiperazine; 2,2,5,5-tetramethylpiperazine; 2-ethylpiperazine; 2,5-diethylpiperazine; and so forth.
• heterocyclic radicals which can replace the group: are: aziridine; pyrrolidine; piperidine; morpholine; thiomorpholine; piperazine; 4-methylpiperazine; 4-ethylpiperazine; and so forth.
• the saline products of general formula (I) can be synthesized by reacting one mole of the 2,4,6-triamino-1,3,5-triazine derivative of general formula (II): where the substituents from R to R5 have the aforedefined meaning, with one mole of cyanuric acid in the presence of a suitable solvent (such as water, methyl alcohol, ethyl alcohol, acetonitrile, and so forth) at a temperature between 0°C and the boiling point of the solvent used.
• a suitable solvent such as water, methyl alcohol, ethyl alcohol, acetonitrile, and so forth
• the saline product formed can be easily separated from the reaction mass by filtration or by distilling the solvent.
• the preferred phosphates are those ammonium polyphosphates of general formula (NH4) n+2 P n O 3+1 in which n is a whole number equal to or greater than 2.
• n is a whole number equal to or greater than 2.
• the molecular weight of the polyphosphates is sufficiently high to ensure low water solubility.
• n varies preferably from 2 to 500.
• composition of the polyphosphates of the aforesaid formula, in which n is a sufficiently large number preferably between 50 and 500, is practically that which corresponds to the metaphosphate formula (NH4PO3) n .
• polyphosphates that known by the commercial name of "Exolit 422” (produced and marketed by the Hoechst Co.) and having the composition (NH4PO3) n in which n is greater than 50.
• NH4PO3 composition in which n is greater than 50.
• Phos-Chek P/40 Monsanto Chemicals
• a further polyphosphate which can be advantageously used, in particular because of its low water solubility, is that known by the commercial name of "Exolit 462” (produced and marketed by the Hoechst Co.) and corresponding to Exolit 422 microencapsulated in melamine-formaldehyde resin.
• Suitable phosphates are those deriving from amines, such as dimethylammonium or diethylammonium phosphate, ethylenediamine phosphate, or melamine ortho or pyrophosphate.
• ammonium phosphonates (mono or poly substituted) deriving from mono or polyphosphonic acids, examples of which are: ethane-1,1,2-triphosphonic acid; 2-hydroxyethane-1,1,2-triphosphonic acid; propane-1,2,3-triphosphonic acid; methylphosphonic acid; ethylphosphonic acid; n-propylphosphonic acid; n-butylphosphonic acid; phenylphosphonic acid; 1-aminoethane-1,1-diphosphonic acid; 1-hydroxyethane-1,1-diphosphonic acid; 1-hydroxydodecane-1,1-diphosphonic acid; phosphonoacetic acid; 2-phosphonopropionic acid; 3-phosphonopropionic acid; 2-phosphonobutyric acid; 4-phosphonobutyric acid; aminotris(methylenephosphonic) acid; ethylenediaminetetra(methylenephosphonic) acid; hexamethylenediaminet
• dienes most commonly present in said elastomeric copolymers are butadiene, ethylidene-norbonene and 1,4-hexadiene.
• ABS acrylonitrile/butadiene/styrene
• SAN styrene/acrylonitrile copolymers
• polyurethane polyethyleneterephthalate
• polybutyleneterephthalate polybutyleneterephthalate
• polyamides polyamides
• the self-extinguishing compositions of the present invention can be prepared by known methods, for example by firstly intimately mixing the ammonium or amine phosphate and/or phosphonate with one or more salts of general formula (I) in finely ground form (preferably with particles less than 70 ⁇ m), then adding the mixture obtained to the polymer in a turbomixer to form a homogeneous mixture, which is extruded and granulated.
• the granulated product obtained in this manner can be transformed into various articles by any of the known moulding methods.
• the flame-retardant additives can also be used in fire-retardant paints.
• the mixture is heated to 40°C and stirred until a solution is obtained, after which 284 g of a 30 wt% aqueous ammonia solution are added over a period of 1 hour 30 minutes while maintaining the temperature at 40°C.
• the solution is then heated to 45°C and maintained at this temperature for 4 hours.
• the mixture is heated to boiling and maintained under reflux for 4 hours.
• the mass is heated to boiling and maintained under reflux for 10 hours.
• the temperature is raised to 20°C and maintained at this value for 1 hour, after which it is raised to 35-40°C, and 40 g of sodium hydroxide dissolved in 100 cm3 of water are added over about 3 hours.
• the reaction mass is heated to 60°C and this temperature maintained for 2 hours.
• the mass is heated to boiling and maintained under reflux for 2 hours, after which 12 g of sodium hydroxide dissolved in 50 cm3 of water are added over about 3 hours.
• Boiling is maintained for a further 2 hours, after which it is cooled to room temperature.
• the aqueous solution is treated with three 300 cm3 portions of methylene chloride.
• the organic extracts are pooled, dried and distilled.
• the mass is heated to boiling and maintained under reflux for 4 hours.
• the mixture is heated to 65-70°C and maintained at this temperature for 2 hours. It is then heated to boiling and maintained under reflux for 1 hour.
• the mass is heated to boiling and maintained under reflux for 14 hours.
• the suspension is heated to 120°C and 302 g of the ethyl ester of N-piperazinecarboxylic acid are added over 1 hour.
• the mixture is maintained at 125-130°C for 2 hours, after which it is cooled to room temperature and the formed product is filtered off, the filter cake being washed firstly with xylene and then abundantly with water.
• the mixture is heated to 95°C and maintained under agitation at this temperature for 6 hours.
• the squeezed filter cake is taken up in a 2 litre beaker with 500 cm3 of water, and a 50 wt% aqueous sodium hydroxide solution added under agitation until pH 11 is attained.
• the mixture is left under agitation for a further 1 hour, after which the formed product is filtered off and washed abundantly on the filter with water.
• the mass is heated to boiling and maintained under reflux for 8 hours.
• the temperature is maintained at 0-3°C for a further 3 hours, after which the aqueous phase is separated.
• the mixture is heated to 50°C and maintained for 7 hours at this temperature. It is allowed to cool to room temperature, the product obtained is filtered off and washed with water.
• the mixture is heated to boiling and maintained under reflux for 3 hours.
• the mass is cooled, the product filtered off and the filter cake washed with water.
• the mass is heated to boiling and maintained under reflux for 10 hours.
• Table 3 shows the results of thermogravimetric analysis (T.G.A.) of some of the salts of general formula (I) described in the examples of the present invention, compared with those of the corresponding 2,4,6-triamino-1,3,5-triazine derivatives of general formula (II).
• the thermal stability of these products was determined by evaluating the weight lost on temperature increase.
• thermobalance A DU PONT Model 951-9900 thermobalance was used, operating with an air rate of 5 litres/hour, a heating rate of 20°C/minute within the temperature range of 20-600°C, and a product quantity of about 10 mg.
• Test pieces in the form of plates of about 3 mm thickness were prepared by moulding mixtures of granular polymer and additives in a MOORE plate press, operating for 7 minutes at a pressure of 40 kg/cm3.
• the level of self-extinguishing was determined on the plates obtained in this manner by measuring the oxygen index (L.O.I. in accordance with ASTM D-2863/77) in a Stanton Redcroft apparatus, and applying the "Vertical Burning Test" which makes it possible the material to be classified in three classes, namely 94 V-0, 94 V-1 and 94 V-2 in accordance with the UL 94 standards (published by the Underwriters Laboratories, USA).
• Table 4 shows the values obtained using an isotactic polypropylene in flake form with a melt flow index of 12 and with 96 wt% insoluble in boiling n-heptane.
• Table 5 shows the values obtained using a low density polyethylene in granular form with a melt flow index of 7; a polystyrene in granular form containing 5 wt% of butadiene rubber and with a melt flow index of 9; a polyester thermoplastic polyurethane (ESTANE 54600 R by Goodrich) and polyether thermoplastic polyurethane (ESTANE 58300 R by Goodrich) in granular form of density 1.19 and 1.10 g/cm3 respectively; an ethylene-propylene elastomer copolymer containing 45 wt% of polypropylene; and an acrylonitrile-butadiene-styrene terpolymer with a density of 1.06 and a melt flow index of 1.6 and containing about 40% of acrylonitrile and styrene and 20% of butadiene.
• test pieces were prepared and subjected to self-extinguishing tests in the aforedescribed manner.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Fireproofing Substances (AREA)
• Fire-Extinguishing Compositions (AREA)

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• 1991
  • 1991-12-04 IT ITMI913253A patent/IT1252632B/it active IP Right Grant
• 1992
  • 1992-12-01 DE DE69209984T patent/DE69209984T2/de not_active Expired - Fee Related
  • 1992-12-01 US US07/983,977 patent/US5331030A/en not_active Expired - Fee Related
  • 1992-12-01 AT AT92203706T patent/ATE136916T1/de not_active IP Right Cessation
  • 1992-12-01 AU AU29806/92A patent/AU659892B2/en not_active Ceased
  • 1992-12-01 EP EP92203706A patent/EP0545496B1/fr not_active Expired - Lifetime
  • 1992-12-01 DK DK92203706.4T patent/DK0545496T3/da active
  • 1992-12-03 CA CA002084498A patent/CA2084498A1/fr not_active Abandoned
  • 1992-12-04 JP JP4350599A patent/JPH05247261A/ja not_active Withdrawn

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